CN105714139B - Copper-graphite alkene composite material and preparation method thereof - Google Patents
Copper-graphite alkene composite material and preparation method thereof Download PDFInfo
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- CN105714139B CN105714139B CN201610096701.9A CN201610096701A CN105714139B CN 105714139 B CN105714139 B CN 105714139B CN 201610096701 A CN201610096701 A CN 201610096701A CN 105714139 B CN105714139 B CN 105714139B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The present invention relates to a kind of copper graphene composite material and preparation method thereof, including graphene and copper, it is characterised in that the graphene is distributed on laminated structure in Copper substrate, and the distribution density of the graphene is 100 pieces/centimetre2To 3000 pieces/centimetre2.It is preferred that the graphene content is 0.01%~0.30wt%, surplus Cu.The present invention adds graphene in copper and copper graphene composite material is made, and Copper substrate can make the electric conductivity of the composite material close to fine copper as conductive bodies, and graphene is improved as reinforced phase, tensile strength and yield strength performance；Therefore the copper graphene composite material can be widely applied to consumer electronics, electrical, aerospace, high ferro, lead frame and electronic connector preparation field；Preparation method provided by the present invention is suitble to industrialization, large-scale production.
Description
Technical field
The present invention relates to a kind of copper-graphite alkene composite materials and preparation method thereof.
Background technology
With necks such as aerospace, traffic, mechanical industry, derived energy chemical, communication, electrical, power electronics and national defense industry
The rapid development in domain, industrial quarters are higher and higher to the electric conductivity requirement of copper or copper alloy.In order to obtain highly conductive copper or copper
Alloy material, domestic and international scientific circles have carried out extensive research, and it is strong to have developed Kufil, aluminum oxide dispersion with industrial circle
Change high-conductivity copper alloys material and the composite materials such as copper.It will although these alloys or composite material can meet highly conductive performance
It asks, but cannot be widely applied since these materials contain noble metal or preparation process complexity, these materials.Industrial quarters
To electric conductivity, the demand of the relatively simple copper alloy of excellent and preparation process or its composite material is more and more urgent.
Graphene is carbon atom with sp2Hydridization connection monoatomic layer form New Two Dimensional atomic crystal, valence band with
Conduction band intersects in fermi level, and it is zero to show the property of semiconductor and energy gap, and carrier shows one at fermi level
The linear dispersion relation of kind, has peculiar property：Intensity is up to 130GPa, thermal conductivity is up to 5150J/ (mK), carrier moves
Shifting rate reaches 1.5 × 104cm2·V-1·s-1, transparency about 97.7%, specific surface area theoretical value 2630m2/ g, Young's modulus
About 1100GPa.
The research and development of existing copper-graphite alkene composite material, are substantially all in the improvement for concentrating on electric conductivity, it is subsequent into
Type processing performance is all undesirable, and this exactly forms the application bottleneck of copper-graphite alkene composite material；Existing preparation side simultaneously
Method inevitably brings Impurity Nickel into, influences the chemical composition and microstructure of copper-graphite alkene composite material, so as to comprehensive to its
Performance is closed to impact.
Invention content
The technical problems to be solved by the invention be for the prior art present situation provide one kind conduct electricity very well, mechanical property
It can be better than fine copper and the good copper-graphite alkene composite material of processing performance.
Another technical problem to be solved by this invention be for the prior art present situation provide one kind conduct electricity very well,
Mechanical property is better than the preparation method of fine copper and the good copper-graphite alkene composite material of processing performance.
Technical solution is used by the present invention solves above-mentioned technical problem：The copper-graphite alkene composite material, including graphite
Alkene and copper, it is characterised in that the graphene is distributed on laminated structure in Copper substrate, and the distribution density of the graphene is 100
Piece/centimetre2To 3000 pieces/centimetre2。
The graphene content is 0.01%~0.30wt%, surplus Cu.
The preparation method of above-mentioned copper-graphite alkene composite material, it is characterised in that include the following steps：
1) copper powder and graphene that grain size is 450 nanometers~550 nanometers are subjected to ball milling in argon atmosphere, make two
Person is uniformly mixed；The Ball-milling Time is preferably 2~4 hours.
2) hot pressed sintering is carried out under protection of argon gas, and sintering pressure is 4 tons~8 tons, and sintering temperature is 850 DEG C~1050
DEG C, the sintered heat insulating time is 3 hours~6 hours；
When pressure is less than 4 ton hours, even if sintering temperature, more than 1050 DEG C, mixed-powder is after the sintering of 6 hours or more
Complete blank can not be sintered into, blank is chipping after being taken out from sintering furnace.When pressure is more than 8 ton hours, sintering mold holds
It is easily chipping.Therefore the sintering pressure of the present invention takes 4 tons~8 tons.When sintering temperature is less than 850 DEG C, even if using 8 tons
Pressure, and be sintered 6 hours or more, blank is chipping after the completion of sintering, does not form an entirety.When sintering temperature is more than
At 1050 DEG C, copper powder particle grows up to form coarse copper particle in blank after the completion of sintering, influences copper-graphite alkene composite wood
The microstructure of material.
3) hot isostatic pressing is carried out at 850 DEG C~1050 DEG C, pressure medium is done with argon gas, the pressure of hot isostatic pressing is
160MPa~200MPa, soaking time are 3 hours~6 hours.
When the pressure of hot isostatic pressing is less than 160MPa, even if sintering temperature is more than 6 small higher than 1050 DEG C, sintering time
When, the graphene distribution density of copper-graphite alkene composite material blank does not change after hot isostatic pressing, illustrates that pressure is less than
During 160MPa, hot isostatic pressing does not help the graphene distribution density for improving composite material blank；When the pressure of hot isostatic pressing
During more than 200MPa, copper-graphite alkene composite material blank is by 850 DEG C of heat preservations, 3 hours hot isostatic pressings with keeping the temperature 6 by 1050 DEG C
The hour graphene distribution density of hot isostatic pressing is equal.When holding temperature is less than 850 DEG C, pressure and guarantor using more than 200MPa
Temperature 6 hours or more, the graphene distribution density of copper-graphite alkene composite material blank is still relatively low；When holding temperature is more than 1050
DEG C when, the copper particle after hot isostatic pressing in copper-graphite alkene composite material blank is grown up phenomenon.The hot isostatic pressing time is less than 3
Hour, the graphene distribution density of copper-graphite alkene composite material blank improves unobvious；The hot isostatic pressing time more than 6 hours,
Copper particle in copper-graphite alkene composite material blank is grown up.
Preferably, the hot pressed sintering process is as follows：It vacuumizes first, when vacuum degree reaches≤10-2After Pa, with 10 ± 1
DEG C/min speed be warming up to after the sintering temperature and start heat preservation and timing.
The present invention makes nano level copper powder be uniformly mixed with graphene using the method that ball milling mixes powder, then hot pressing is pre-sintered
The method of hot isostatic pressing prepares the blank of copper-graphite alkene composite material, wherein hot isostatic pressing step can greatly improve graphene with
The binding ability of Copper substrate, graphene are tightly combined with Copper substrate, and avoid the oxidation of copper, and the bond strength of the two carries significantly
Height, graphene are evenly distributed in laminated structure in Copper substrate, and it is close to be distributed the graphene in copper-graphite alkene composite material
Degree is controllable；The prepared hot and cold processability of copper-graphite alkene blank that obtains is excellent, can be prepared by way of hot and cold pressure processing
Copper-graphite alkene composite material wire rod connects so as to prepare consumer electronics, electrical, aerospace, high ferro, lead frame and electronics
Strong height leads the section bars such as copper-graphite alkene composite material wire rod in needed for plug-in unit preparation field.
The present invention adds graphene in copper and copper-graphite alkene composite material is made, and Copper substrate can be used as conductive bodies to make this
The electric conductivity of composite material is close to fine copper, and graphene is obtained as reinforced phase, tensile strength and yield strength performance
It improves；Therefore the copper-graphite alkene composite material can be widely applied to consumer electronics, electrical, aerospace, high ferro, lead frame
With electronic connector preparation field；Preparation method provided by the present invention is suitble to industrialization, large-scale production.
Description of the drawings
Fig. 1 is the electromicroscopic photograph that blank prepared by the embodiment of the present invention 1 amplifies 30,000 times.
Specific embodiment
The present invention is described in further detail below in conjunction with attached drawing embodiment.
Embodiment 1
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.01wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2Start to be warming up to 850 DEG C with the speed of 10 ± 1 DEG C/min after Pa, Isothermal sinter, soaking time 3 hours is entirely burnt
Pressure during knot to mixed-powder application is 4 tons.After the completion of hot pressed sintering, blank is taken out and carries out hot isostatic pressing, heat etc.
For static pressure using argon gas as applying pressurised gas, heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa,
At a temperature of 850 DEG C, 3 hours are kept the temperature, obtains 50 blanks of Φ.
Surface polishing treatment is carried out to blank, the sample room of scanning electron microscope is put into, carries out Surface scan under vacuum conditions, obtain
The electromicroscopic photograph arrived is as shown in Figure 1.
Label 1 is graphene in Fig. 1, and rest part is Copper substrate.The distribution density of graphene is 102 pieces/centimetre2, stone
The distribution density of black alkene measures under scanning electron microscope in the method for area percentage, using same in subsequent embodiment and comparative example
The method of sample surveys the distribution density of graphene.
Made 50 blanks of Φ carry out stretch process after hot extrusion prepares 12 line bases of Φ and prepare wire rod, the diameter of made wire rod
For 5.0mm.
Embodiment 2
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.15wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2Start to be warming up to 850 DEG C with the speed of 10 ± 1 DEG C/min after Pa, Isothermal sinter keeps the temperature 3 hours, entire sintered
Pressure in journey to mixed-powder application is 4 tons.After the completion of hot pressed sintering, blank is taken out and carries out hot isostatic pressing, hot isostatic pressing
Using argon gas as applying pressurised gas, heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, temperature
850 DEG C, soaking time 3 hours obtains 50 blanks of Φ, and the distribution density of graphene is 1488 pieces/centimetre2.Made 50 blanks of Φ
Stretch process, which is carried out, after hot extrusion prepares 12 line bases of Φ prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 3
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.30wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2986 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 4
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.05wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1050 DEG C of sintering temperature, 6 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 8 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 200MPa, 1050 DEG C of temperature, soaking time 6 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 498 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 5
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.10wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1000 DEG C of sintering temperature, 5 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 6 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 180MPa, 1000 DEG C of temperature, soaking time 5 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 991 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 6
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.17wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1050 DEG C of sintering temperature, 6 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 8 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 200MPa, 1050 DEG C of temperature, soaking time 6 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 1697 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 7
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.20wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：950 DEG C of sintering temperature, 4 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 950 DEG C of temperature, soaking time 4 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 1983 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 8
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.25wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：900 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 900 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2485 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 9
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.28wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 2 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2783 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 10
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.08wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 4 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1050 DEG C of sintering temperature, 6 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 8 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 200MPa, 1050 DEG C of temperature, soaking time 6 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 797 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 11
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.03wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 4 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1050 DEG C of sintering temperature, 6 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 8 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 200MPa, 1050 DEG C of temperature, soaking time 6 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 294 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
Embodiment 12
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.23wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 2 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2281 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.
The electron microscope photo scanning of blank prepared by embodiment 2 to embodiment 12 is substantially the same manner as Example 1.
Comparative example 1
Using fine copper as raw material, graphene is not added, 50 round billets of Φ are prepared using vacuum casting, made blank is through hot extrusion
Progress stretch process prepares wire rod, a diameter of 5.0mm of made wire rod after preparing 12 line bases of Φ.(the addition of embodiment 1
The copper-graphite alkene composite material wire rod of 0.01wt% graphenes) it is compared with comparative example 1 it is found that declining in conductivity unconspicuous
In the case of, addition graphene can greatly improve its tensile strength and yield strength.
Comparative example 2
Using the copper powder that grain size is 500 nanometers as raw material, graphene is not added, doing protective gas using argon gas carries out ball milling
Mixed powder, Ball-milling Time are 3 hours.After the completion of ball milling mixes powder, mixed-powder is packed into hot pressing in the glove box of argon filling gas shielded
It is sintered in mould, the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, when vacuum degree reaches≤10-2Start after Pa
Heating (heating rate is 10 ± 1 DEG C/min), starts heat preservation and timing after temperature is raised to sintering temperature.Hot-pressing sintering technique
For：850 DEG C of sintering temperature, 3 hours sintered heat insulating time to the pressure that mixed-powder applies are 4 tons in entire sintering process.Heat
After the completion of pressure sintering, blank is taken out and carries out hot isostatic pressing, for hot isostatic pressing using argon gas as applying pressurised gas, heat temperature raising speed is 10
±1℃/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 hours.Made 50 blanks of Φ warp
Progress stretch process prepares wire rod, a diameter of 5.0mm of made wire rod after hot extrusion prepares 12 line bases of Φ.(the addition of embodiment 1
The copper-graphite alkene composite material wire rod of 0.01wt% graphenes) it is compared with comparative example 2 it is found that add graphene in copper, conductivity
Decline unobvious, but its tensile strength and yield strength can be greatly improved.
Comparative example 3
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.15wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：830 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 1482 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.It is compared with embodiment 2 it is found that in graphene content
In the case of identical, when the temperature of hot pressed sintering is less than temperature range of the invention, even if other technological parameters are identical, phase
Than for, performance is relatively low.
Comparative example 4
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.23wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 2 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 830 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2137 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.It is compared with embodiment 12 it is found that working as hot isostatic pressing
Temperature less than the present invention temperature range when, even if graphene content is identical with other technological parameters, copper-graphite alkene composite wood
The performance of stockline material can also decline.
Comparative example 5
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.20wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：1070 DEG C of sintering temperature, 4 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 950 DEG C of temperature, soaking time 4 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 1962 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.It is compared with embodiment 7 it is found that in graphene content
And in the case that other technological parameters are identical, when hot pressed sintering temperature is more than the temperature range of the present invention, performance also can under
Drop.
Comparative example 6
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.28wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 2 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 1070 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 2635 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.It is compared with embodiment 9 it is found that in graphene content
And in the case that other technological parameters are identical, when the temperature of hot isostatic pressing is more than the temperature range of the present invention, performance is substantially
Decline.
Comparative example 7
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.31wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, blank take out carry out hot isostatic pressing, hot isostatic pressing using argon gas as applying pressurised gas,
Heat temperature raising speed is 10 ± 1 DEG C/min.The technique of hot isostatic pressing is：Pressure 160MPa, 850 DEG C of temperature, soaking time 3 is small
When, 50 blanks of Φ are obtained, the distribution density of graphene is 3096 pieces/centimetre2.Made 50 blanks of Φ prepare 12 lines of Φ through hot extrusion
Stretch process is carried out after base and prepares wire rod, a diameter of 5.0mm of made wire rod.It is compared with embodiment 3 it is found that in technological parameter phase
With in the case of, when graphene content is more than the composition range of the present invention, tensile strength, yield strength and conductivity start
It declines to a great extent.
Comparative example 8
Using the copper powder and graphene that grain size is 500 nanometers as raw material, graphene content is 0.30wt%, is done using argon gas
Protective gas carries out ball milling and mixes powder, and Ball-milling Time is 3 hours.After the completion of ball milling mixes powder, the handle in the glove box of argon filling gas shielded
Mixed-powder is fitted into hot pressed sintering mould, and the hot pressed sintering mould equipped with mixed-powder is fitted into hot-pressed sintering furnace, works as vacuum degree
Reach≤10-2(heating rate is 10 ± 1 DEG C/min) is started to warm up after Pa, starts to keep the temperature after temperature is raised to sintering temperature and count
When.Hot-pressing sintering technique is：850 DEG C of sintering temperature, 3 hours sintered heat insulating time are applied to mixed-powder in entire sintering process
The pressure added is 4 tons.After the completion of hot pressed sintering, for blank without hot isostatic pressing, the distribution density of graphene is 1863 pieces/li
Rice2.Although with hot extrusion technique such as embodiment 3, but only carry out hot pressed sintering and do not carry out the base of hot isostatic pressing
Material can not carry out subsequent hot extrusion processing, and serious fragmentation occurs in hot extrusion process, it is compound can not to prepare copper-graphite alkene
Line of material base.
The test of tensile strength, yield strength and conductivity is carried out to wire rod prepared by each embodiment and comparative example, as a result
As shown in table 1.
Wherein, tensile strength, yield strength and elongation percentage are according to GB/T 228.1-2010《Metal material stretching test the 1st
Part：Room temperature test method》It is carried out on electronic universal testing machine for mechanical properties；Resistivity measurement method is according to GB/T
3048.2-2007《Electric wire electrical performance test method part 2：Metal material resistivity test》It is enterprising in resistance meter
Resistivity, is converted into conductivity (%IACS) by row.
Table 1
■ --- it is chipping during hot extrusion, wire rod can not be processed, therefore without performance data.
Claims (4)
1. copper-graphite alkene composite material, including graphene and copper, it is characterised in that the graphene is distributed on copper with laminated structure
In matrix, the distribution density of the graphene is 100 pieces/centimetre2To 3000 pieces/centimetre2；
The graphene content is 0.01%~0.30wt%, surplus Cu；
The copper-graphite alkene meets the tensile strength of material for 280~400MPa, 260~400MPa of yield strength, and conductivity is
90~99.9%IACS, elongation percentage are 30~38.5%.
2. the preparation method of copper-graphite alkene composite material as described in claim 1, it is characterised in that include the following steps：
1) copper powder and graphene that grain size is 450 nanometers~550 nanometers are subjected to ball milling in argon atmosphere, make the two mixed
It closes uniform；
2) hot pressed sintering is carried out under protection of argon gas, and sintering pressure is 4 tons~8 tons, and sintering temperature is 850 DEG C~1050 DEG C, is burnt
It is 3 hours~6 hours to tie soaking time；
3) carry out hot isostatic pressing at 850 DEG C~1050 DEG C, pressure medium done with argon gas, the pressure of hot isostatic pressing for 160MPa~
200MPa, soaking time are 3~6 hours.
3. preparation method according to claim 2, it is characterised in that the hot pressed sintering process is as follows：It vacuumizes first,
When vacuum degree reaches≤10-2After Pa, it is warming up to after the sintering temperature with 10 ± 1 DEG C/min of speed and starts heat preservation and timing.
4. preparation method according to claim 3, it is characterised in that the Ball-milling Time is 2~4 hours.
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| CN107245590B (en) * | 2017-06-14 | 2019-04-23 | 上海电缆研究所有限公司 | Copper-graphite alkene composite material and preparation method |
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| CN109332705B (en) * | 2018-10-29 | 2021-01-12 | 南京工程学院 | Graphene modified copper-molybdenum-copper composite material and preparation method thereof |
| CN109351976B (en) * | 2018-10-29 | 2020-07-10 | 无锡乐普金属科技有限公司 | Copper-molybdenum copper-copper composite material for semiconductor high-power device and preparation method thereof |
| CN112349667A (en) * | 2019-08-09 | 2021-02-09 | 昆山微电子技术研究院 | Preparation method of graphene/copper composite metal interconnection line |
| CN110512187B (en) * | 2019-09-02 | 2020-08-21 | 上海交通大学 | Two-dimensional material reinforced metal matrix composite material and continuous preparation method thereof |
| CN111145960B (en) * | 2019-12-19 | 2022-05-17 | 中车工业研究院有限公司 | High-strength high-conductivity copper-based composite material and preparation method thereof |
| CN111020279B (en) * | 2019-12-26 | 2021-08-17 | 浙江杭机新型合金材料有限公司 | High-strength high-conductivity copper-graphite composite material and preparation method thereof |
| CN112359244B (en) * | 2020-10-21 | 2022-02-22 | 有研工程技术研究院有限公司 | High-strength high-conductivity graphene copper composite wire and preparation method thereof |
| CN113046608A (en) * | 2021-03-04 | 2021-06-29 | 王安华 | Graphene metal, preparation method and product thereof |
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